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CHEM01200604009 Sreejith Kaniyankandy - Homi Bhabha ...

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28<br />

known examples are oxidation of a metal in atmosphere, electron transfer across a metal<br />

semiconductor interface etc [1. 43].<br />

Figure 1.11. Reactant and Product Potential Energy Curves<br />

One of the first approaches towards ET theory was put forward by Libby where he<br />

pointed to the importance of Franck-Condon principle in electron transfer involving same<br />

inorganic ions in different coordination environments like Fe(CN) . The schematic diagram<br />

of how Franck-Condon principle plays a role is given below.<br />

The schematic in fig 1.11 shows that on electron transfer between Fe (III) and Fe (II),<br />

the solvent environment around the ions remains unchanged as rate of electron transfer<br />

compared to reorganization of solvent molecules is faster. This energy difference arising<br />

from a wrong solvent environment acts as solvation barrier. Additionally it can be clearly<br />

seen from the figure that bond length in Fe (III) is shorter compared to Fe (II) therefore<br />

electron transfer lead to a wrong vibrational environment, this factor also contribute towards<br />

4-<br />

6

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